Transforming exciton dynamics in perovskite nanocrystal through Mn doping.

Zn-alloyed CsPb(Cl/Br)3 perovskite nanocrystals (PNCs) have been synthesized and used as a model system for Mn doping in order to understand the effect of Mn doping on exciton dynamics. While keeping the PL emission maximum and PLQY of both PNC samples nearly the same, the radiative decay rate of the host band decreases ∼6.5 times and the non-radiative decay rate increases ∼2.5 times upon Mn doping. Unlike reports in the literature in which the dopant emission decreases to near-zero, in the present case we observe ∼5.5-fold enhancement of the integrated PL intensity of the dopant emission when the temperature decreases from 290 K to 190 K. Interestingly, the FWHM of the host PL emission band increases with a decrease in temperature from 290 K to 190 K. A higher value of phonon energy in PNC2 (58 ± 2 meV) in comparison to CsPbBr3 has been noted. The low magnitude of the Huang-Rhys factor indicates less electron phonon coupling for the Mn-doped PNC system. Temperature-dependent dopant PL decay exhibits biexponential decay behaviour with time constants τ1 = 450-540 µs and τ2 = 1.1-1.2 ms. With a decrease in temperature from 290 K to 190 K, the amplitude of the faster component decreases from 80% to 60%; concomitantly, the amplitude of the slower component increases from 20% to 40%. Ultrasensitive single-particle spectroscopic analyses reveal that, although the probability density distributions (PDDs) of the durations of both ON and OFF events of PNC1 could be fitted with a truncated inverse power law (TIPL), however, for PNC2, both PDDs could be fitted with an inverse power law (IPL). A comparatively lower value of the power law exponent mON indicates a higher probability of longer ON events for PNC1 than for PNC2. Truncation in the PDDs of both ON and OFF events has been observed for PNC1, but not in the PDDs of either ON or OFF events for PNC2. The presence of shallow trap states is responsible for the truncation for PNC1, whereas the presence of deep dopant states does not allow truncation in the host PL emission of PNC2. All these observations clearly demonstrate that Mn doping transforms the host PL exciton dynamics for Zn-alloyed Mn-doped CsPb(Cl/Br)3 PNCs very significantly.

Beneficial Intrinsic Hole Trapping and Its Amplitude Variation in a Highly Photoluminescent Toxic-Metal-Free Quantum Dot.

Intrinsic hole trapping as well as hole detrapping have not been observed for any quantum dot (QD) or perovskite nanocrystal (PNC) system. Moreover, amplitude variation of intrinsic hole trapping (or detrapping) has not been reported at all for any QD or PNC system. However, for a CuInS2-based core/alloy-shell (CAS) QD system, (a) both intrinsic hole trapping and detrapping have been observed and (b) very significant amplitude variations of hole trapping (∼16 to ∼42%) and hole detrapping (∼44 to 23%) have been observed. Unlike detrimental electron trapping, hole trapping has been shown to be beneficial, having a direct correlation toward increasing PLQY to 96%. Simultaneous electron and hole trapping has been shown to be quite beneficial for the CuInS2-based CAS QD system leading to the longest ON time (∼130 s) for which a nontoxic metal-based QD remains only in the ON-state without blinking.

Medical Tourism in Tripura: Issues & Opportunities.

Medical tourism in India has an immense scope, primarily due to the unavailability or inaccessibility of medical treatment in border areas of native countries, such as Bangladesh and Myanmar. Also, the significantly low cost of complex surgery and highly skilled doctors are the most significant factors for driving tourism in India. Thus, there is a vast scope for entrepreneurship in this area. On the other hand, it is being covered by lush forests, lakes, and hills. This study aims to develop a model to increase the population of outbound or international patients and their families for medical services. Tripura, being topographically easily accessible for patients from Bangladesh and Myanmar, can be commuted within hours. The study was cross-sectional, and a purposive sampling technique was used. The data was collected using a 5-point rating scale specifically constructed to understand the factors enhancing medical tourism. Various hospitals that provide medical services to domestic (other states in India) & international clients, tourism agencies, and relevant sources have contributed to this study.

Evaluation of adverse drug reactions of chemotherapeutic agents used in advanced non-small cell lung cancer - experience from a rural tertiary care institution in North Eastern India.

BACKGROUND: Lung cancer is one of the major causes of morbidity and mortality both in developed and developing countries. Adverse drug reactions (ADRs) are inevitable, albeit unwanted aspects of cancer chemotherapeutic agents used in lung cancer. AIM AND OBJECTIVES: To determine common ADRs and the severity of ADRs of different chemotherapeutic agents used in non-small cell lung cancer (NSCLC) patients. MATERIALS AND METHODS: The study was conducted among purposively selected 160 patients who had undergone chemotherapy for lung carcinoma. Clinical records of NSCLC patients were reviewed and data related to the socio-demographic and clinic-therapeutic profiles of patients were collected. ADRs were graded according to the Common toxicity criteria (CTC) grading. Data analysis was done using the IBM-SPSS software and presented using the principle of descriptive statistics. Relationships between ADRs and drug regimens were determined using Chi-square tests considering a 95% confidence interval and P value ≤ 0.05 as significant. RESULT: Among 160 patients, 78.8% were males and 21.3% were females. The mean age was 59.15 ± 10.6 years, illness duration was 7.5 ± 10.6 months, and treatment duration was 4.4 ± 0.91 months. The overall mortality rate and systemic toxicity of the paclitaxel-carboplatin combination were the lowest. Almost an equal proportion of moderate to severe changes in parameters such as myelosuppression, anemia, thrombocytopenia, alopecia, skin changes, allergic reaction, and peripheral neuropathy, were observed with all chemotherapeutic regimens. Gemcitabine-carboplatin regimen was associated with a higher proportion of altered liver enzymes, electrolyte imbalance, diarrhea, pleural effusion, and renal toxicities. CONCLUSION: There was a high prevalence of ADRs with different chemotherapeutic agents. Early detection of these ADRs may help in minimizing the damage by either modifying the dose or changing the offending agent.

Excitation-Energy-Dependent Photoluminescence Quantum Yield is Inherent to Optically Robust Core/Alloy-Shell Quantum Dots in a Vast Energy Landscape.

The importance of alloy-shelling in optically robust Core/Alloy-Shell (CAS) QDs has been described from structural and energetic aspects. Unlike fluorescent dyes, both Core/Shell (CS) and CAS QDs exhibit excitation-energy-dependent photoluminescence quantum yield (PLQY). For both CdSe and InP CAS QDs (with metal- and nonmetal-based alloy-shelling, respectively), with increasing excitation energy, (a) the ultrafast rise-time or relaxation-time to the band-edge increases and (b) the magnitude of the normalized bleach signal decreases. Ultrasensitive single-particle spectroscopic investigation results showed that with decreasing excitation energy, (a) the fraction of ON events increases, (b) the ratio of exciton-detrapping rate/trapping rate increases, and (c) the extent of beneficial hole trapping increases. A relative decrease in PLQY with increasing excitation energy is much less pronounced in CAS QDs than in CS QDs. Unless trap states are removed completely especially in the higher-energy landscape, PLQY will remain inherently dependent on excitation energy for QDs in the vast energy landscape. When reporting the PLQY of QDs, the magnitude of the excitation energy must be mentioned.

Ultrafast dynamics and ultrasensitive single particle spectroscopy of optically robust core/alloy shell semiconductor quantum dots.

A "one-pot one-step" synthesis method of Core/Alloy Shell (CAS) quantum dots (QDs) offers the scope of large scale synthesis in a less time consuming, more economical, highly reproducible and high-throughput manner in comparison to "multi-pot multi-step" synthesis for Core/Shell (CS) QDs. Rapid initial nucleation, and smooth & uniform shell growth lead to the formation of a compositionally-gradient alloyed hetero-structure with very significantly reduced interfacial trap density in CAS QDs. Thus, interfacial strain gets reduced in a much smoother manner leading to enhanced confinement for the photo-generated charge carriers in CAS QDs. Convincing proof of alloy-shelling for a CAS QD has been provided from HRTEM images at the single particle level. The band gap could be tuned as a function of composition, temperature, reactivity difference of precursors, etc. and a high PLQY and improved photochemical stability could be achieved for a small sized CAS QD. From the ultrafast exciton dynamics in CdSe and InP CAS QDs, it has been shown that (a) the hot exciton thermalization/relaxation happens in <500 fs, (b) hot electron trapping dynamics occurs within a ∼1 ps time scale, (c) band edge exciton trapping occurs within a 10-25 ps timescale and (d) for CdSe CAS QDs the hot hole gets trapped in about 35 ps. From fast PL decay dynamics, it has been shown that the amplitude of the intermediate time constant can be correlated with the PLQY. A model has been provided to understand these ultrafast to fast exciton dynamical processes. At the ultrasensitive single particle level, unlike CS QDs, CdSe CAS QDs have been shown to exhibit (a) constancy of PLmax (i.e. no bluing) and (b) constancy of PL intensity (i.e. no bleaching) of the single CAS QDs for continuous irradiation for one hour under an air atmosphere. Thus, CAS QDs hold the promise of being a superior optical probe in comparison to CS QDs both at the ensemble and at the single particle level, leading to enhanced flexibility of the CAS QDs towards designing and developing next generation application devices.

A retrospective analysis of serological & molecular testing data on dengue fever in Kolkata & adjacent districts during 2016-2019.

Background & objectives: Regional Virus Research and Diagnostic Laboratory established at ICMR-National Institute of Cholera and Enteric Diseases (NICED) regularly receives samples for dengue screening and serotyping from patients of acute febrile illness (AFI) from Kolkata and adjacent districts. In this study, data over a three year period (August 2016-July 2019) was retrospectively analyzed to provide insight into the epidemiological trends of dengue fever in this region. Methods: Serological screening of dengue was performed by detection of NS1 antigen and/or immunoglobulin M (IgM) antibody. Dengue serotyping was done by conventional or real-time reverse transcriptase-PCR. The data were analyzed to describe the distribution of dengue with respect to age of patient, duration of fever on the day of blood collection and month of the year. Zip codes were used for spatial plotting. Results: Out of the 24,474 samples received from Kolkata and its adjacent districts (Hooghly, Howrah, North and South 24 Parganas), 38.3 per cent (95% confidence interval: 37.7-38.9%) samples were screened positive for dengue. The correlation between age and dengue positivity was found to be weak. A combination of dengue NS1 antigen and dengue IgM antibody detection may be a better option for detecting dengue positivity compared to a single test. Most AFI cases were tested from August to November during the study period, with maximum dengue positivity noted during September (45.9%). The predominant serotype of 2016, dengue virus serotype 1 (DENV-1), was almost entirely replaced by DENV-2 in 2017 and 2018. Interpretation & conclusions: Dengue continues to be an important cause of AFI in the region and round-the-year preventive measures are required for its control. Serotype switching is alarming and should be monitored routinely.

Structure-based discovery of (S)-2-amino-6-(4-fluorobenzyl)-5,6,11,11a-tetrahydro-1H-imidazo[1',5':1,6]pyrido[3,4-b]indole-1,3(2H)-dione as low nanomolar, orally bioavailable autotaxin inhibitor.

Inhibition of extracellular secreted enzyme autotaxin (ATX) represents an attractive strategy for the development of new therapeutics to treat various diseases and a few inhibitors entered in clinical trials. We herein describe structure-based design, synthesis, and biological investigations revealing a potent and orally bioavailable ATX inhibitor 1. During the molecular docking and scoring studies within the ATX enzyme (PDB-ID: 4ZGA), the S-enantiomer (Gscore = -13.168 kcal/mol) of the bound ligand PAT-494 scored better than its R-enantiomer (Gscore = -9.562 kcal/mol) which corroborated with the reported observation and analysis of the results suggested the scope of manipulation of the hydantoin substructure in PAT-494. Accordingly, the docking-based screening of a focused library of 10 compounds resulted in compound 1 as a better candidate for pharmacological studies. Compound 1 was synthesized from L-tryptophan and evaluated against ATX enzymatic activities with an IC50 of 7.6 and 24.6 nM in biochemical and functional assays, respectively. Further, ADME-PK studies divulged compound 1 as non-cytotoxic (19.02% cell growth inhibition at 20 µM in human embryonic kidney cells), metabolically stable against human liver microsomes (CLint  = 15.6 µl/min/mg; T1/2  = 113.2 min) with solubility of 4.82 µM and orally bioavailable, demonstrating its potential to be used for in vivo experiments.

Near-Ergodic CsPbBr3 Perovskite Nanocrystal with Minimal Statistical Aging.

Optical robustness, uniformity, ergodicity, statistical aging, etc. dictate the applicability of nanocrystals. Based on a series of multimodal statistical analyses such as the Kolmogorov-Smirnov test, Lévy statistics, etc., we demonstrate that for CsPbBr3 perovskite nanocrystals (PNCs): (a) the extent of heterogeneity in the quality and associated physical processes is minimal; (b) the optical robustness is very high, and (c) indeed, a single PNC can depict optical behavior of its ensemble. In addition, toward prospective applications, an optically robust CsPbBr3 PNC exhibits (i) near-ergodicity and (ii) minimal statistical aging, which are extremely vital and complementary to its high defect tolerance.

Unravelling halide-dependent charge carrier dynamics in CsPb(Br/Cl)3 perovskite nanocrystals.

With an increasing bromide content in CsPb(Br/Cl)3 perovskite nanocrystals (PNCs), the steady state photoluminescence quantum yield value increases from 28% to 50% to 76%. Ultrafast transient absorption analyses reveal that the normalized band edge population increases more than two-fold on excitation at the band edge with increasing bromide content, and the hot exciton trapping time increases from 450 fs to 520 fs to 700 fs with increasing bromide content. Ultrasensitive single particle spectroscopic analyses reveal that the peak of the ON fraction distribution increases from 0.65 to 0.75 to 0.85 with increasing bromide content. More specifically, the percentage of PNCs with the ON fraction >75% increases four fold from 24% to 50% to 98% with increasing bromide content. Moreover, the ratio of the detrapping rate and trapping rate increases more than 25 fold with an increase in bromide content, signifying the excitons remaining in the trap state for a smaller time with increasing bromide content. In order to standardize the measurement and analyses, all these three PNCs have the same size and shape, and all the excitations have been made at the same energy above the band edge for all three PNCs and for both ultrafast transient absorption and ultrasensitive single particle measurements.

Near-Unity Photoluminescence Quantum Yield and Highly Suppressed Blinking in a Toxic-Metal-Free Quantum Dot.

There is no literature report of simultaneously achieving near-unity PLQY (ensemble level) and highly suppressed blinking (ultrasensitive single-particle spectroscopy (SPS) level) in a toxic-metal-free QD. In this Letter we report accomplishing near-unity PLQY (96%) and highly suppressed blinking (>80% ON fraction) in a toxic-metal-free CuInS2/ZnSeS Core/Alloy-Shell (CAS) QD. In addition, (i) gigantic enhancement of PLQY (from 15% (Core) to 96% (CAS QD)), (ii) ultrahigh stability over 1 year without significant reduction of PLQY at the ensemble level, (iii) high magnitude (nearly 3 times) of electron detrapping/trapping rate, and (iv) very long ON duration (∼2 min) without blinking at the SPS level enable this ultrasmall (∼3.3 nm) CAS QD to be quite suitable for single-particle tracking/bioimaging. A model explaining all these excellent optical properties has been provided. This ultrabright CAS QD has been successfully utilized toward fabrication of low-cost microcontroller-based stable and bright yellow and white QD-LEDs.

Extent of Shallow/Deep Trap States beyond the Conduction Band Minimum in Defect-Tolerant CsPbBr3 Perovskite Quantum Dot: Control over the Degree of Charge Carrier Recombination.

Perovskite quantum dots (PQDs) are known to be defect-tolerant, possessing a clean band gap with optically inactive benign defect states. However, we show that there exist significant deep trap states beyond the conduction band minimum, although the extent of shallow trap states is observed to be minimal. The extent of deep trap states beyond the conduction band minimum seems to be significant in PQDs; however, the extent is less than that of even optically robust CdSe- and InP-based core/alloy-shell QDs. In-depth analyses based on ultrafast transient absorption and ultrasensitive single-particle spectroscopic investigations decode the underlying degree of charge carrier recombination in CsPbBr3 PQDs, which is quite important for energy applications.

Donor/acceptor chromophores-decorated triazolyl unnatural nucleosides: synthesis, photophysical properties and study of interaction with BSA.

Much effort has been put forth to develop unnatural, stable, hydrophobic base pairs with orthogonal recognition properties and study their effect on DNA duplex stabilisation. Our continuous efforts on the design of fluorescent unnatural biomolecular building blocks lead us to the synthesis of some triazolyl donor/acceptor unnatural nucleosides via an azide-alkyne 1,3-dipolar cycloaddition reaction as a key step, which we want to report herein. We have studied their photophysical properties and found interesting solvatochromic fluorescence for two of the nucleosides. Photophysical interactions among two donor-acceptor ß-nucleosides as well as a pair of α/ß-nucleosides have also been evaluated. Furthermore, we have exploited one of the fluorescent nucleosides in studying its interaction with BSA with the help of UV-visible and steady state fluorescence techniques. Our design concept is based on the hypothesis that a pair of such donor/acceptor nucleosides might be involved in π-stacking as well as in photophysical interactions, leading to stabilization of the DNA duplex if such nucleosides can be incorporated into short oligonucleotide sequences. Therefore, the designed bases may find application in biophysical studies in the context of DNA.

Single step concomitant concentration, purification and characterization of two families of lipopeptides of marine origin.

The extracellular biosurfactant product secreted by a marine bacterium was concentrated and purified directly from the fermentation broth in a single step by ultrafiltration (UF) employing YM 30 kDa (UF-I) and Omega 10 kDa (UF-II) polyethersulfone membranes. The optimum operating pressure required for both membranes, UF-I and UF-II, were found to be 30 and 35 psi, respectively. The biosurfactant from the fermentation broth was recovered in higher amounts using UF-II (89%) than using UF-I (73%). An analysis of the critical micelle concentrations (CMC) of the recovered lipopeptides showed a lower CMC value of 15 mg L⁻¹ for the UF-II product, indicating higher degree of purity (83%) when compared to that of the UF-I product (78%). The ultrafiltered products were characterized using Fourier transformed infrared spectroscopy and matrix-assisted laser desorption ionization time of flight mass spectral analysis, which demonstrated the presence of two families of lipopeptides.

Biosurfactant production and growth kinetics of bacteria in a designer marine medium: improved physiochemical properties.

A combinatorial screening strategy was adopted for the development of a suitable medium for enhanced biosurfactant production by a marine strain. As a result, a modified marine medium (MMM) was developed, which contained urea and strontium chloride besides other salts important for the growth of marine bacteria. This medium supported growth, evident from a higher maximum growth rate value of 0.42 h(-1) and an enhanced biosurfactant production of 2.58 g/L. The critical micelle concentration (CMC) was determined for the biosurfactants obtained from all tested media combinations. The biosurfactant produced with this medium was stable at high temperature (100 °C), a wide range of pH (5-11) and salt concentration of 5-35%. The emulsifying activity and stability of the biosurfactant obtained using MMM was better than the biosurfactant obtained using conventional media. This biosurfactant with improved physiochemical properties is suitable for a wide range of applications in industry and for marine environmental cleaning.

Two accounts of the colonised "other" in South Asia re-exploring alterity.

Taking examples from South Asia, this article shows how British colonial knowledge about the non-European "other" hinged substantially on the participation of sections of that other, especially in the context of liminal groups, for whom no ready standardised formula of identification was available. Development of a colonial episteme often involved active intervention from the colonised body, thereby dispelling any strict notion of coloniser-colonised alterity and mere top-down governance. This process of identity construction took place in several arenas and also involved negotiations in courts of law, where rival sections of the amorphous colonised body fought for competing ideals of selfhood. Complementing this legal construction were ethnographic formulations, internally diverse, and often relating to broader politico-intellectual concerns and debates of the Empire, at different planes in different ways. The article explicates their theoretical bases and practical modalities.

Microbial surfactants of marine origin: potentials and prospects.

Marine environment occupies the vast majority of the earth's surface and is a rich source of highly potent and active compounds. In recent years, microbial surfactants and emulsifiers have been reported from marine microflora. Surfactant and emulsifier molecules having diverse chemical nature such as exopolysaccharides, carbohydrate-lipid-protein complexes or glycolipopeptide, glycolipids, lipopeptides, phospholipids and ornithine lipids have been reported from various marine bacteria. These surface-active agents have been found to possess good emulsification and stabilization potentials for various lipophilic compounds such as aliphatic, aromatic and polyaromatic hydrocarbons and their uptake and degradation by the microorganisms. Few biosurfactant types such as glycolipids and lipopeptides have also been found to possess valuable biological activities. Surface-active agents from marine environments thus have tremendous potential to be used in industrial processes, for environmental remediation and as drugs.

Artificial neural network modeling and genetic algorithm based medium optimization for the improved production of marine biosurfactant.

A nonlinear model describing the relationship between the biosurfactant concentration as a process output and the critical medium components as the independent variables was developed by artificial neural network modeling. The model was optimized for the maximum biosurfactant production by using genetic algorithm. Based on a single-factor-at-a-time optimization strategy, the critical medium components were found to be glucose, urea, SrCl(2) and MgSO(4). The experimental results obtained from a statistical experimental design were used for the modeling and optimization by linking an artificial neural network (ANN) model with genetic algorithm (GA) in MATLAB. Using the optimized concentration of critical elements, the biosurfactant yield showed close agreement with the model prediction. An enhancement in biosurfactant production by approximately 70% was achieved by this optimization procedure.

High-performance liquid chromatography purification of biosurfactant isoforms produced by a marine bacterium.

A marine Bacillus strain produced biosurfactant during its growth in a defined glucose-containing medium. An efficient method for separation and purification of biosurfactant isoforms was developed and optimized in high-performance liquid chromatography (HPLC) by manipulating solvent gradient program and flow rates. Starting with an initial run time of 60 min, the final optimized method had a significantly reduced run time of 20 min. By using this method, all the surface-active isoforms (fractions A-D) were eluted within 12 min of elution with much shortened retention time of each component. The purity levels of the isoforms were enhanced using the optimized method as evident from their lower CMC values. Among the four surface-active fractions, antimicrobial action was solely displayed by HPLC fraction A. FTIR analysis revealed all the HPLC fractions to be lipopeptide in nature and MALDI-ToF mass spectral analysis showed that these belonged to the fengycin family containing C(15), C(16), and C(17) fengycins.

Biosurfactant of marine origin exhibiting heavy metal remediation properties.

The present study was aimed at elucidating the role of biosurfactant product isolated from a marine bacterium in removing heavy metals from heavy metal containing solutions. In this study, metal removal was biosurfactant-mediated. Efficiency of metal removal depended on the concentration of the metal as well as that of the biosurfactant. At a concentration 5x, the critical micelle concentration (CMC), almost complete removal of 100 ppm of lead and cadmium occurred. Atomic absorption spectroscopy (AAS) studies also showed metal removal at a concentration less than the CMC in contrast to earlier findings that only micelles are involved in metal removal. Fourier transform infrared spectroscopy (FTIR) and transmission electron microscopy (TEM) equipped with energy dispersive X-ray spectroscopy (EDS) further substantiated these findings.